This invention relates to a polymerization catalyst composition and to its use in the polymerization of alkenes (olefins), in particular alpha olefins. The present invention relates to methods of making a series of organic compounds, the methods for making metal-containing catalyst systems employing these organic compounds, and a polymerization process for employing the catalysts. In particular, the present invention relates to polymerization catalysts containing electron-withdrawing amide ligands.
The use of metal-containing compounds as catalysts for the polymerization of small organic molecules to high molecular weight polymer is an area of intense interest.
Polymerization processes of olefins, such as the production of polyethylene from ethene, whereby homogeneous catalyst systems of the Ziegler-Natta type are used, are well known. Several factors are important in determining the utility of a particular catalyst system. Firstly, the system must show good catalytic activity, that is, each molecule of catalyst should be capable of joining together many hundreds, thousands or even millions of monomer units before it is subject to deactivation. Secondly, the catalyst should provide good control over the molecular weight of the resultant polymer chain and give a narrow molecular weight distribution of polymer chains. Thirdly, the catalyst should provide good control over the molecular architecture of the polymer which it produces. In the polymerization of propylene, for example, the catalyst may be capable of aligning all of the pendant methyl groups onto the same side of the polymer chain (isotactic), while another catalyst may constrain them to alternate in a left-right-left-right sequence as the polymer chain is formed (syndiotactic). 
Fourthly, the catalyst should, if desired, allow the incorporation into the polymer chain of two or more different monomer types and the formation of co-polymers containing monomers of widely differing structures.
The polymerization of hydrocarbon monomers containing a double bond (i.e. alkenes, or olefins) is one of the largest volume processes carried out by the chemical industry. The field of olefin polymerization is dominated by the use of catalysts containing the Group IV metals (titanium, zirconium and hafnium) and to a lesser extent chromium and vanadium. In recent years, the use of Group IV metal catalysts containing one or, more usually, two cyclopentadienyl-type ligands (such as the complex depicted in I) has become extremely important due to their high catalytic activity, and extremely good control over both molecular weight distribution and molecular architecture of the resulting polymer. 
These catalysts are being investigated extensively by major chemical companies. However, a drawback of these catalyst systems is their inability to co-polymerize olefins with many of the readily-available co-monomers desired by industry (e.g. vinyl chloride, carbon monoxide). In many cases the co-monomers are oxygen-containing species which coordinate very strongly to the metal center and prevent the coordination and polymerization of the olefin.
Thus a considerable amount of work is being focused upon developing alternatives to the bis-cyclopentadienyl ligand system for the early transition metals and lanthanides. One option which has been explored is to employ diimine ligands on a transition metal center (II), and this type of complex has been found to be extremely useful for the co-polymerization of olefins with olefinic esters. 
Another possibility which has been investigated is to replace one or both of the cyclopentadienyl ligands with a bulky oxygen-donor ligand such as an aryloxide (as shown in III and IV). 
However, previous work has shown that the introduction of these relatively electron-donating ligands in place of cyclopentadienyl ligands greatly attenuates the catalytic activity of a metal center (see Clark et al., Organometallics 1996, 15, 949 and Butcher et al., Organometallics 1996, 15, 1488). This is believed to be a result of build-up of electron density at the metal center which reduces the electrophilicity of the metal.
In order to counteract this undesirable effect, the present catalyst system was developed involving: (i) changing the ligand donor atom from oxygen to nitrogen, which has only one rather than two lone pairs capable of donation to a metal center; (ii) placing highly electron-withdrawing groups onto the nitrogen atom to further reduce the amount of electron density donated to the metal center; and, (iii) as catalytic activity for olefin polymerization has been reported to be increased by linking or xe2x80x9ctying-backxe2x80x9d two ligands to form a single bidentate ligand (see Fendrick et al., Organometallics 1988, 7, 1828), this principle was applied and two amine ligands are linked together to form a single ligand containing two xe2x80x94NH groups: 
While a few recent patents and papers have described the use of such xe2x80x9ctied-backxe2x80x9d bis-amine ligands in the formulation of olefin polymerization catalysts, the substituents employed on the nitrogen atoms were alkyl or aryl groups, which serve to provide steric bulk but do not greatly influence the electronic characteristics of the ligand. For example, in WO 92/12162 there are disclosed catalyst systems for the polymerization of alpha olefins, comprising as a first component an amido transition metal compound of the general formula (A) 
wherein M is zirconium, hafnium or titanium, N is a nitrogen atom having three substituents, X is any univalent anionic ligand, R is a hydrocarbyl, T is a covalent hydrocarbyl bridging group containing a Group 14 or 16 element such as a silicon radical, y is 1 or 0 and z is 2xe2x88x92y, and as a second component alumoxane. The disclosed effect of this group of catalysts is the production of solid stereoregular polyolefins having a molecular weight well in excess of 100,000.
In WO 96/27439 there are disclosed catalyst systems for the oligomerization of ethene to higher olefins, comprising as a first component a compound represented by the general formula (B) 
wherein M is zirconium, hafnium or titanium; each N is a three coordinate nitrogen atom; each Y is Si, Ge or Sn; each X is, independently, a hydride or R; each R is, independently, a hydrocarbyl one or more carbon atoms of which may be substituted by an element selected from Si, O, P, N and S; Q is a neutral Lewis base and m is a number from 0 to 2; or a dimer thereof. The disclosed effect of this group of catalysts is the production of olefins having a chain length within the range of 4 to 24 carbon atoms.
The present invention combines the concept of the bis-amine ligand with the use of electron-withdrawing or electron-donating substituents so as to influence the electronic as well as the steric character of the ligand.
There has now been found a number of novel catalyst compositions based on bridged or unbridged amido transition metal or lanthanide compounds which are effective in the polymerization of alpha olefins to high molecular weight polymers. These catalyst compositions are distinguished from the prior art by the ability to greatly affect the electrophilicity of the metal center by introducing electron-withdrawing substituents directly onto the nitrogen atoms. Compared to the best catalyst compositions based on metallocenes, these novel compositions are distinguished by the ease of preparation of the complexes from readily available precursors.
The present invention is useful for performing polymerization reactionsxe2x80x94most notably the polymerization of olefins, such as ethylene and propylene, but is also applicable to the polymerization of cyclic carbonate monomers to form polycarbonates. The focal point of the invention is a catalyst system which utilizes electron-withdrawing amide ligands attached to a transition or lanthanide metal center.
The present invention also provides classes of bridged bis-amine ligands which are C2-symmetric (chiral), which may be produced either by placing an inherently chiral group onto the nitrogen atom attached to the metal, or by placing inherently chiral groups onto the bridging portion of the ligand, or by attaching non-chiral groups to the bridging portion in such a way as to produce chiral centers at one or more of the bridging atoms. Once placed onto a metal center, these ligands are capable of influencing the stereochemistry of polymerization of prochiral olefins so as to produce highly stereospecific (isotactic or syndiotactic) polyolefins. The three-dimensional shape of the ligand must be designed so as to influence the stereochemistry of olefin insertion. In a typical bridged bis-amide ligand system, the points of attachment of groups on the bridging atoms are considerably removed in distance from the point of olefin coordination to the metal center (as shown below): 
Therefore the C2-symmetric (chiral) bis-amide ligands may incorporate large, rigid groups (such as, e.g., polycyclic aromatic hydrocarbons or polycyclic saturated hydrocarbons) which xe2x80x98transferxe2x80x99 the chirality of the bridging fragment to the vicinity of the coordinated olefin (the example below features a phenanthrene group): 
The present invention provides a catalyst composition comprising a compound represented by the general formula (III) 
wherein M is a Group 3-10 metal or a lanthanide metal; each N is a three-coordinate nitrogen atom; B is a bridging atom which is normally C, Si, Ge or Sn; L is a neutral Lewis base and y is a number from 0 to 3; each X is independently a hydride, a halogen or C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl, alkylaryl or Si(R3)3 or N(R3)2; each R3 being independently chosen from the group of C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl; when M is a trivalent lanthanide or tlivalent Group 3-10 metal then one X is absent; when M is a divalent lanthanide or divalent Group 3-10 metal then both X are absent; R1 and R2 are electron-withdrawing groups such as partially or wholly halogenated aryl (C6HxZ5xe2x88x92x, x=0-5, Z is a halogen), halogenated alkyl (CjZ2j+1, j=1-10, Z is a halogen), sulfonyl (SO2CkZ2k+1, k=1-10, Z is a halogen), sulfonated aryl (C6HxS5xe2x88x92x, x=0-5, S is a sulfonyl group of the type SO2ChZ2h+1, h=1-10, Z is a halogen) or Si(R3)3; each E is independently H, F, C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl with any of these alkyl or aryl groups bearing one or more halogen atoms; or a dimer of formula (III); and a second component.
Preferably M is a Group 4 metal or a lanthanide element.
Preferably B is carbon or silicon.
Preferably the halogenated electron-withdrawing groups contain at least one fluorine substituent.
Examples of the neutral Lewis base L are diethyl ether, tetrahydrofuran, dioxane, diethylamine and dimethylaniline.
The dimer of the compound of formula (III) is according to the general formula (IV) 
wherein the symbols are as defined above, z being 0 or 1.
Preferred compounds of formula (III) according to the invention are [bis(pentafluorophenylamino)dimethylsilane]metal dimethyl, {Me2Si[N(C6F5)]2}MMe2, [bis(pentafluorophenylamino)dimethylsilane]metal dibenzyl, Me2Si[N(C6F5)]2}M(CH2Ph)2, [bis(pentafluorophenylamino)dimethylsilane]metal bis(trimethylsilylmethyl), Me2Si[N(C6F5)]2}M(CH2SiMe3)2, [bis(Pentafluorophenylamino)dimethylsilane]metal bis(neopentyl), {Me2Si[N(C6F5)]2}M(CH2CMe3)2, [bis(pentafluorophenylamino)dimethylsilane]metal dihydride, {Me2Si[N(C6F5)]2}MH2 in which M is zirconium, hafnium, or titanium, [bis(pentafluorophenylamino)dimethylsilane]metal methyl, {Me2Si[N(C6F5)]2}MMe, [bis(pentafluorophenylamino)dimethylsilane]metal benzyl, {Me2Si[N(C6F5)]2}M(CH2Ph) [bis(pentafluorophenylamino)dimethylsilane]metal bis(trimethylsilyl)methyl, {Me2Si[N(C6F5)]2}M[CH(SiMe3)2], [bis(Pentafluorophenylamino)dimethylsilane]metal (trimethylsilyhmethyl), {Me2Si[N(C6F5)]2}M(CH2SiMe3), [bis(pentafluorophenylamino)dimethylsilane]metal neopentyl, Me2Si[N(C6F5)]2}M(CH2CMe3), [bis(pentafluorophenylamino)dimethylsilane]metal hydride, {Me2Si[N(C6F5)]2}MH, in which M is scandium, yttrium or a lanthanide element, [bis(3,5-bis(trifluoromethyl)phenylamino)dimiethylsilane]metal dimethyl, {Me2Si[N-3,5-(CF3)2C6H3]2}MMe2, [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal dibenzyl, {Me2Si[N-3,5-(CF3)2C6H3]2}M(CH2Ph)2, [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal bis(trimethylsilylmethyl), {Me2Si[N-3,5-(CF3)2C6H3]2}M(CH2SiMe3)2, [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal bis(neopentyl), {Me2Si[N-3,5-(CF3)2C6H3]2}M(CH2CMe3)2, [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal dihydride, {Me2Si[N-3,5-(CF3)2C6H3]2)}MH2, in which M is zirconium, hafnium, or titanium, [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal methyl, {Me2Si[N-3,5-(CF3)2C6H3]2}MMe, [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal benzyl, {Me2Si[N-3,5-(CF3)2C6H3]2}M(CH2Ph), [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal bis(trimethylsilyl)methyl, {Me2Si[N-3,5-(CF3)2C6H3]2}M[CH(SiMe3)2], [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal (trimethylsilylmethyl), {Me2Si[N-3,5-(CF3)2C6H3]2}M(CH2SiMe3), [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal neopentyl, {Me2Si[N-3,5-(CF3)2C6H3]2}M(CH2CMe3), [bis(3,5-bis(trifluoromethyl)phenylamino)dimethylsilane]metal hydride, {Me2Si[N-3,5-(CF3)2C6H3]2}MH, in which M is scandium, yttrium or a lanthanide element, [bis(pentafluorophenylamino)diphenylstannane]metal dimethyl, {Ph2Sn[N(C6F5)]2}MMe2, [bis(pentafluorophenylamino)diphenylstannane]metal dibenzyl, {Ph2Sn[N(C6F5)]2}M(CH2Ph)2, in which M is zirconium, hafnium, or titanium, [bis(3,5-bis(trifluoromethyl)phenylamino)diphenylstannane]metal bis(trimethylsilyl)methyl, (Ph2Sn[N-3,5-(CF3)2C6H3]2}M[CH(SiMe3)2] in which M is scandium, yttrium or a lanthanide element, [bis(pentafluorophenylamino)bis(pentafluorophenyl)silane]metal dimethyl, {(C6F5)2Si[N(C6F5)]2}MMe2, [bis(pentafluorophenylamino)bis(pentafluorophenyl)silane]metal dibenzyl, {(C6F5)2Si[N(C6F5)]2}M(CH2Ph)2, in which M is zirconium, hafnium, or titanium, [bis(pentafluorophenylarino)bis(pentafluorophenyl)silane]metal bis(trimethylsilyl)methyl, {(C6F5)2Si[N(C6F5)]2}M[CH(SiMe3)2], in which M is scandium, yttrium or a lanthanide element, [bis(trifluoromethylsulfonylamino)dimethylsilane]metal dimethyl, {Me2Si[N(SO2CF3)]2}MMe2, [bis(trifluoromethylsulfonylamino)dimethylsilane]metal dibenzyl, {Me2Si[N(SO2CF3)]2}M(CH2Ph)2, in which M is zirconium, hafnium, or titanium, [bis(trifluoromethylsulfonylamino)dimethylsilane]metal bis(trimethylsilyl)methyl, {Me2Si[N(SO2CF3)]2}M[CH(SiMe3)2], in which M is scandium, yttrium or a lanthanide element, [(2,6dimethylphenylamino)pentafluorophenylaminomethylene]metal dimethyl, [CH2(NC6F5)(N-2,6-Me2C6H3)]MMe2, [(2,6-dimethylphenylamino)pentafluorophenylaminomethylene]metal dibenzyl, [CH2(NC6F5)(N-2,6-Me2C6H3)]M(CH2Ph)2, in which M is zirconium, hafnium, or titanium, [(2,6-dimethylphenylamino)pentafluorophenylaminomethylene]metal bis(trimethylsilyl)methyl, [CH2(NC6F5)(N-2,6-Me2C6H3)]M[CH(SiMe3)2], in which M is scandium, yttrium or a lanthanide element, [(2,6-di-iso-propylphenylamino)(3,5-bis(trifluoromethyl)phenylaminomethylene]metal dimethyl, [CH2(N-3,5-(CF3)2C6H3)(N-2,6-i-Pr2C6H3)]MMe2, [(2,6-di-iso-propylephenylamino)(3,5-bis(trifluoromethyl)phenylaminomethylene]metal dibenzyl, [CH2(N-3,5-(CF3)2C6H3)(N-2,6-i-Pr2C6H3)]M(CH2Ph)2, in which M is zirconium hafnium, or titanium, [(2,6-di-iso-propylphenylamino)(3,5-bis(trifluoromethyl)phenylaminomethylene]metal bis(trimethylsilyl)methyl, [CH2(N-3,5-(CF3)2C6H3)(N-2,6-i-Pr2C6H3)]M[CH(SiMe3)2], in which M is scandium yttrium or a lanthanide element.
The present invention further provides a catalyst composition comprising a compound represented by the general formula (V) 
wherein M, N, L, y, X, R1 and R2 are as defined above; each B is independently a substituted carbon atom; each A is independently CH, CH2, CF, CF2, N or NH; x is a number from 0 to 10 such that the Bxe2x80x94Bxe2x80x94Ax loop may represent C6-C15 aryl or heteroaryl, C3-C10 cycloalkyl or alkylaryl or halogenated derivatives thereof; or a dimer of formula (V); and a second component.
Preferably M is a Group 4 metal or a lanthanide element.
Preferably B is carbon.
Preferably the halogenated electron-withdrawing groups contain at least one fluorine substituent.
Examples of the neutral Lewis base L are diethyl ether, tetrahydrofuran, dioxane, diethylamine and dimethylaniline.
The dimer of formula (V) is according to general formula (VI) 
wherein the symbols are defined above, z being 0 or 1.
Preferred compounds of formula (V) according to the invention are [1,2-Bis(pentafluorophenylamino)benzene]metal dimethyl, [(1,2-(C6F5N)2C6H4]MMe2[1,2-Bis(pentafluorophenylamino)benzene]metal dibenzyl, [(1,2-(C6F5N)2C6H4]M(CH2Ph)2[1,2-Bis(pentafluorophenylamino)benzene]metal bis(neopentyl), [(1,2-(C6F5N)2C6H4]M(CH2CMe3)2, [1,2-Bis(pentafluorophenylamino)benzene]metal dihydride, [(1,2-(C6F5N)2C6H4]MH2, in which M is zirconium, hafnium, or titanium, [1,2-Bis(pentafluorophenylamino)benzene]metal methyl, [(1,2-(C6F5N)2C6H4]MMe, [1,2-Bis(pentafluorophenylamino)benzene]metal benzyl, [(1,2-(C6F5N)2C6H4]M(CH2Ph), [1,2-Bis(pentafluorophenylamino)benzene]metal bis(trimethylsilyl)methyl, [(1,2-(C6F5N)2C6H4]M[CH(SiMe3)2], [1,2-Bis(pentafluorophenylamino)benzene]metal hydride, [(1,2-(C6F5N)2C6H4]MH, in which M is scandium, yttrium or a lanthanide element, [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal dimethyl, [(1,2-(2,6-Me2C6H3N)2C6F4]MMe2, [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal dibenzyl, [(1,2-(2,6-Me2C6H3N)2C6F4]M(CH2Ph)2, [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal bis(neopentyl), [(1,2-(2,6-Me2C6H3N)2C6F4]M(CH2CMe3)2, [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal dihydride, [(1,2-(2,6-Me2C6H3N)2C6F4]MH2, in which M is zirconium, hafnium, or titanium, [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal methyl, [(1,2-(2,6-Me2C6H3N)2C6F4]MMe, [1,2-Bis(2,6-dimethylphenylamino)tetrafuorobenzene]metal benzyl, [(1,2-(2,6-Me2C6H3N)2C6F4]M(CH2Ph), [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal bis(trimethylsilyl)methyl, [(1,2-(2,6-Me2C6H3N)2C6F4]M[CH(SiMe3)2], [1,2-Bis(2,6-dimethylphenylamino)tetrafluorobenzene]metal hydride, [(1,2-(2,6-Me2C6H3N)2C6F4MH, in which M is scandium, yttrium or a lanthanide element, [R,R-1,2-Bis(2,6-di-iso-propylphenylamino)cyclohexane]metal dimethyl, [1R,2R-(2,6-i-Pr2C6H3N)2C6H10]MMe2, [R,R-1,2-Bis(2,6-di-iso-propylphenylamino)cyclohexane]metal dibenzyl, [1R,2R-(2,6-i-Pr2C6H3N)2C6H10]M(CH2Ph)2, [R,R-1,2-Bis(2,6di-iso-propylphenylamino)cyclohexane]metal dihydride, [1R,2R-(2,6-i-Pr2C6H3N)2C6H10]MH2, in which M is zirconium, hafnium, or titanium, [R,R-1,2-Bis(2,6-di-iso-propylphenylamino)cyclohexane]metal bis(trimethylsilyl)methyl, [1R,2R-(2,6-i-Pr2C6H3N)2C6H10]M[CH(SiMe3)2], [R,R-1,2-Bis(2,6-di-iso-propylphenylamino)cyclohexane]metal hydride, [1R,2R-(2,6-i-Pr2C6H3N)2C6H10]MH, in which M is scandium, yttrium or a lanthanide element, [R,R-1,2-Bis(pentafluorophenylamino)cyclohexane]metal dimethyl, [1R,2Rxe2x80x94(C6F5N)2C6H10]MMe2, [R-1,2-Bis(pentafluorophenylamino)cyclohexane]metal dibenzyl, [1R,2Rxe2x80x94(C6F5N)2C6H10]M(CH2Ph)2, [R,R-1,2-Bis(pentafluorophenylamino)cyclohexane]metal dihydride, [1R,2Rxe2x80x94(C6F5N)2C6H10]MH2, in which M is zirconium, hafnium, or titanium, [R,R-1,2-Bis(pentafluorophenylamino)cyclohexane]metal bis(trimethylsilyl)methyl, [1R,2Rxe2x80x94(C6F5N)2C6H10]M[CH(SiMe3)2], [R,R-1,2-Bis(pentafluorophenylamino)cyclohexane]metal hydride, [1R,2Rxe2x80x94(C6F5N)2C6H10]MH, in which M is scandium, yttrium or a lanthanide element, [R,R-1,2-Bis(3,5-bis(trifluoromethyl)phenylamino)-1,2-diphenylethane]metal dimethyl, [1R,2R-(3,5-(CF3)2C6H3N)2Ph2C2H2]MMe2, [RR-1,2-Bis(3,5-bis(trifluoromethyl)phenylamino)-1,2-diphenylethane]metal dibenzyl, [1R,2R-(3,5-(CF3)2C6H3N)2Ph2C2H2]M(CH2Ph)2, [R,R-1,2-Bis(3,5-bis(trifluoromethyl)phenylamino)-1,2-diphenylethane]metal dihydride, [1R,2R-(3,5-(CF3)2C6H3N)2Ph2C2H2]MH2, in which M is zirconium, hafnium, or titanium, [R,R-1,2-Bis(3,5-bis(trifluoromethyl)phenylamino)-1,2-diphenylethane]metal bis(trimethylsilyl)methyl, (1R,2R-(3,5-(CF3)2C6H3N)2Ph2C2H2]M[CH(SiMe3)2], [R,R-1,2-Bis(3,5-bis(trifluoromethyl)phenylamino)-1,2-diphenylethane]metal hydride, [1R,2R-(3,5-(CF3)2C6H3N)2Ph2C2H2]MH, in which M is scandium, yttrium or a lanthanide element.
The present invention further provides a catalyst composition comprising a, compound represented by the general formula (VII) 
wherein M, N, L, y, X, R1 and R2 are as defined above; each B is independently a substituted carbon atom; A, C and D are independently C, CH, CH2, CF, CF2, N or NH; x is a number from 0 to 10 such that the Bxe2x80x94Bxe2x80x94Bxe2x80x94Axxe2x80x94Dxxe2x80x94Cx system may represent C3-C10 bicycloalkyl, C6-C15 diaryl, C6-C15 heterodiaryl or fluorinated derivatives thereof; or a dimer of formula (VII); and a second component.
Preferably M is a Group 4 metal or a lanthanide element.
Preferably A, B, C and D are carbon.
Preferably the halogenated electron-withdrawing groups contain at least one fluorine substituent.
Examples of the neutral Lewis base L are diethyl ether, tetrahydrofuran, dioxane, diethylamine and dimethylaniline.
The dimer of formula (VII) is according to general formula (VIII) 
wherein the symbols are defined above, z being 0 or 1.
Preferred compounds of formula (VD) according to the invention are [1,8-bis(pentafluorophenylamino)naphthalene]metal dimethyl, [1,8-(C6F5N)2C10H6]MMe2, [1,8-bis(pentafluorophenylamino)naphthalene]metal dibenzyl, [1,8-(C6F5N)2C10H6]M(CH2Ph)2, [1,8-bis(pentafluorophenylamino)naphthalene]metal dihydride, [1,8-(C6F5N)2C10H6]MH2, in which M is zirconium, hafnium, or titanium, [1,8-bis(pentafluorophenylamino)naphthalene]metal bis(trimethylsilyl)methyl, [1,8-(C6F5N)2C10H6]M[CH(SiMe3)2], [1,8-bis(pentafluorophenylamino)naphthalene]metal hydride, [1,8-(C6F5N)2C10H6]MH, in which M is scandium, yttrium or a lanthanide element, [1,3-bis(3,5-bis(trifluoromethyl)phenylamino)propane]metal dimethyl, [(CH2)3-1,3-(N-3,5-(CF3)2C6H3)2]MMe2, [1,3-bis(3,5-bis(trifluoromethyl)phenylamino)propane]metal dibenzyl, [(CH2)3-1,3-(N-3,5-(CF3)2C6H3)2]M(CH2Ph)2, [1,3-bis(3,5-bis(trifluoromethyl)phenylamino)propane]metal dihydride, [(CH2)3-1,3-(N-3,5-(CF3)2C6H3)2]MH2, in which M is zirconium, hafnium, or titanium [1,3-bis(3,5-bis(trifluoromethyl)phenylamino)propane]metal bis(trimethylsilyl)methyl, [(CH2)3-1,3-(N-3,5-(CF3)2C6H3)2]M[CH(SiMe3)2], [1,3-bis(3,5-bis(trifluoromethyl)phenylamino)propane]metal hydride, [(CH2)3-1,3-(N-3,5-(CF3)2C6H3)2]MH, in which M is scandium, yttrium or a lanthanide element, [1,3-bis(pentafluorophenylamino)propane]metal dimethyl, [(CH2)3-1,3-(NC6F5)2]MMe2, [1,3-bis(pentafluorophenylamino)propane]metal dibenzyl [(CH2)3-1,3-(NC6F5)2]M(CH2Ph)2, [1,3-bis(pentafluorophenylamino)propane]metal dihydride, [(CH2)3-1,3-(NC6F5)2]MH2, in which M is zirconium, hafnium, or titanium, [1,3-bis(pentafluorophenylamino)propane]metal bis(trimethylsilyl)methyl, [(CH2)3-1,3-(NC6F5)2]M[CH(SiMe3)2], (1,3-bis(pentafluorophenylamino)propane]metal hydride, [(CH2)3-1,3-(NC6F5)2]MH, in which M is scandium, yttrium or a lanthanide element.
The present invention further provides a catalyst composition comprising a compound represented by the general formula (IX) 
wherein M, N, L, y, X R1 and R2 are as defined above; B is an sp2 hybridized bridging atom which is normally C, Si, Ge or Sn; G is a Group 15 element such as N, P or As; R4 is R1 or C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl; or a dimer of formula (IX); and a second component.
Preferably M is a Group 4 metal or a lanthanide element.
Preferably B is carbon.
Preferably G is nitrogen.
Preferably the halogenated electron-withdrawing groups contain at least one fluorine substituent.
Examples of the neutral Lewis base L are diethyl ether, tetrahydrofuran, dioxane, diethylamine and dimethylaniline.
The dimer of the compound of formula (IX) is according to the general formula (X) 
wherein the symbols are as defined above, z being 0 or 1.
Preferred compounds of formula (D) according to the invention are [N-pentafluorophenyl(bis(2,6-dimethylphenylamino)imine)metal dimethyl, [(C6F5)Nxe2x95x90C(NH-2,6-Me2C6H3)2]MMe2, [N-pentafluorophenyl(bis(2,6-dimethylphenylamino)imine)metal dibenzyl, [(C6F5)Nxe2x95x90C(NH-2,6-Me2C6H3)2]M(CH2Ph)2, [N-pentafluorophenyl(bis(2,6-dimethylphenylamino)imine)metal dihydride, [(C6F5)Nxe2x95x90C(NH-2,6-Me2C6H3)2]MH2, in which M is zirconium, hafnium, or titanium, [N-pentafluorophenyl(bis(2,6-dimethylphenylamino)imine)metal bis(trimethylsilyl)methyl, [(C6F5)Nxe2x95x90C(NH-2,6-Me2C6H3)2]M(CH(SiMe3)2], [N-pentafluorophenyl(bis(2,6-dimethylphenylamino)imine)metal hydride, [(C6F5)Nxe2x95x90C(NH-2,6-Me2C6H3)2]MH, in which M is scandium, yttrium or a lanthanide, N-pentafluorophenylbis(3,5-bis(trifluoromethyl)phenylamino)imine metal dimethyl, [(C6F5)Nxe2x95x90C(NH-3,5CF3)2C6H3)2]MMe2, N-pentafluorophenylbis(3,5-bis(trifluoromethyl)phenylamino)imine metal dibenzyl, [(C6F5)Nxe2x95x90C(NH-3,5-(CF3)2C6H3)2]M(CH2Ph)2, N-pentafluorophenylbis(3,5-bis(trifluoromethyl)phenylamino)imine metal dihydride, [(C6F5)Nxe2x95x90C(NH-3,5-(CF3)2C6H3)2]MH2, in which M is zirconium, hafnium, or titanium, N-pentafluorophenylbis(3,5-bis(trifluoromethyl)phenylamino)imine metal bis(trimethylsilyl)methyl, [(C6F5)Nxe2x95x90CH-3,5-(CF3)2C6H3)2]M[CH(SiMe3)2], N-pentafluorophenylbis(3,5-bis(trifluoromethyl)phenylamino)imine metal hydride, [(C6F5)Nxe2x95x90C(NH-3,5CF3)2C6H3)2]MH, in which M is scandium, yttrium or a lanthanide.
The present invention further provides a catalyst composition comprising a compound represented by the general formula (XI) 
wherein M, N, L, y, X are as defined above; R1, R2, R3 and R4 are independently electron-withdrawing groups such as halogenated aryl (C6HxZ5xe2x88x92x, x=0-4, Z is a halogen), halogenated alkyl (CjZ2j+1, j=1-10, Z is a halogen), sulfonyl (SO2CkZ2k+1, k=1-10, Z is a halogen), sulfonated aryl (C6HxS5xe2x88x92x, x=0-4, S is a sulfonyl group of the type xe2x80x94SO2ChZ2h+1, h=1-10, Z is a halogen); or a dimer of formula (XI); and a second component.
Preferably M is a Group 4 metal or a lanthanide element. Preferably the halogenated electron-withdrawing groups contain at least one fluorine substituent.
Examples of the neutral Lewis base L are diethyl ether, tetrahydrofuran, dioxane, diethylamine and dimethylaniline.
The dimer of the compound of formula (XI) is according to the general formula (XII) 
wherein the symbols are as defined above, z being 0 or 1.
Preferred compounds of formula (XI) according to the invention are Bis(bis(pentafluorophenyl)amino) metal dimethyl, {[(C6F5)2N]2MMe2}, Bis(bis(pentafluorophenyl)amino) metal dibenzyl, {[(C6F5)2N]2M(CH2Ph)2}, Bis(bis(pentafluorophenyl)amino) metal dihydride, {[(C6F5)2N]2MH2}, in which M is zirconium, hafnium, or titanium, Bis(bis(pentafluorophenyl)amino) metal bis(trimethylsilyl)methyl, {[(C6F5)2N]2M[CH(SiMe3)2}, Bis(bis(pentafluorophenyl)amino) metal hydride, {[(C6F5)2N]2MH}, in which M is scandium, yttrium or a lanthanide, Bis(bis(trifluoromethylsulfonyl)amino)metal dimethyl, {[(CF3SO2)2N]2MMe2}, Bis(bis(trifluoromethylsulfonyl) metal dibenzyl, {[(CF3SO2)2N]2M(CH2Ph)2}, Bis(bis(trifluoromethylsulfonyl) metal dihydride, {[(CF3SO2)2N)2MH2}, in which M is zirconium, hafnium, or titanium, Bis(bis(trifluoromethylsulfonyl)amino) metal bis(trimethylsilyl)methyl, {[(CF3SO2)2N]2M[CH(SiMe3)2}, Bis(bis(trifluoromethylsulfonyl)amino) metal hydride, {[(CF3SO2)2N]2MH}, in which M is scandium, yttrium or a lanthanide, Bis[(2,6-di-iso-propylphenyl)(3,5-bis(trifluoromethyl)phenyl)amino metal dimethyl, [(3,5-(CF3)2C6H3)(2,6-Me2C6H3)N]2MMe2, Bis[(2,6-di-iso-propylphenyl)(3,5-bis(trifluoromethyl)phenyl)amino metal dibenzyl, [(3,5-(CF3)2C6H3)(2,6-Me2C6H3)N]2M(CH2Ph)2, Bis[(2,6-di-iso-propylphenyl)(3,5-bis(trifluoromethyl)phenyl)amino metal dihydride, [(3,5-(CF3)2C6H3)(2,6-Me2C6H3)N]2MH2, in which M is zirconium, hafnium, or titanium Bis[(2,6-di-iso-propylphenyl)(3,5-bis(trifluoromethyl)phenyl)amino metal bis(trimethylsilyl)methyl, [(3,5-(CF3)2C6H3)(2,6-Me2C6H3)N]2M[CH(SiMe3)2], Bis[(2,6-di-iso-propylphenyl)(3,5-bis(trifluoromethyl)phenyl)amino metal hydride, [(3,5-(CF3)2C6H3)(2,6-Me2C6H3)N]2MH, in which M is scandium, yttrium or a lanthanide.
The present invention further provides a catalyst composition comprising a compound represented by the general formula (XIII) 
wherein each M is independently a Group 3-10 metal or a lanthanide element; each N is a three-coordinate nitrogen atom; B is a bridging atom which is normally C, Si, Ge or Sn; L is a neutral Lewis base and y is a number from 0 to 3; each X is independently a hydride or C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl, alkylaryl or Si(R3)3 or N(R3)2; each R3 being independently chosen from the group of C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl; when M is a trivalent lanthanide or trivalent Group 3-10 metal then one X on each M is absent; when M is a divalent lanthanide or divalent Group 3-10 metal both X on each M are absent; R1, R2, R3 and R4 are independently electron-withdrawing groups such as halogenated aryl (C6HxZ5xe2x88x92x, x=0-4, Z is a halogen), halogenated allyl (CjZ2j+1, j=1-10, Z is a halogen), sulfonyl (SO2CkZ2k+1, k=1-10, Z is a halogen), sulfonated aryl (C6HxS5xe2x88x92x, x=0-4, S is a sulfonyl group of the type xe2x80x94SO2ChZ2h+1, h=1-10, Z is a halogen); and a second component.
Preferably M is a Group 4 metal or a lanthanide element.
Preferably B is silicon.
Preferably the halogenated electron-withdrawing groups contain at least one fluorine substituent.
Examples of the neutral Lewis base L are diethyl ether, tetrahydrofuran, dioxane, diethylamine and dimethylaniline.
Preferred compounds of formula (XIII) according to the invention are Tetrakis(pentafluorophenylamino)silane dimetal tetramethyl, [(C6F5N)4Si]M2Me4, Tetrakis(pentafluorophenylamino)silane dimetal tetrabenzyl, [(C6F5N)4Si]M2(CH2Ph)4, Tetrais(pentafluorophenylamino)silane dimetal tetrahydride, [(C6F5N)4Si]M2H4, in which M is zirconium, hafnium, or titanium, Tetrakis(pentafluorophenylamino)silane dimetal bis(bis(trimethylsilyl)methyl), [(C6F5N)4Si]M2[CH(SiMe3)2]2, Tetrais(pentafluorophenylamino)silane dimetal dihydride, [(C6F5N)4Si]M2H2, in which M is scandium, yttrium or a lanthanide.
The present invention further comprises a catalyst composition comprising a first component which is a compound according to any of formulas (II), (V), (VII), (IX), (XI) or (XIII) or dimers thereof, and a second component which is capable of providing a bulky and labile anion [A]xe2x88x92 which anion is substantially non-coordinating under the reaction conditions and contains at least one boron atom.
The first and second component together form an ionic compound of the general formula(XIV) 
or, of the general formula (XV) 
wherein the symbols are as defined above.
Examples of the anion [A]xe2x88x92 containing a boron atom are the borates of the general formula [B(R2)4]xe2x88x92, wherein R2 is a hydride, C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl, any of which can be substituted by one or more halogens, such as [B(C6F5)4]xe2x88x92, [R2B(C6F5)3]xe2x88x92, [B(FC6H4)4]xe2x88x92, [R2B(FC6H4)3]xe2x88x92, {B[3,5-(CF3)2C6H3]4}xe2x88x92 and {R2B[3,5-(CF3)2C6H3]3}31 .
The second component can itself be an ionic compound of an anion [A]xe2x88x92 as defined above and a cation. The cation is suitably a proton-donating cation, preferably a quaternary ammonium cation such as tri-n-butylammonium, or dimethylanilinium. Alternatively a cation may be used in the second component which is not proton-donating, such as a metal cation e.g. a silver ion, or a triphenylcarbenium ion.
The second component can also be a neutral strongly Lewis acidic compound which is capable of abstracting one of the radicals X of the first component, thereby also contributing an anion [A]xe2x88x92 as defined above.
Preferred second components in the catalytic composition according to the invention are the ionic compounds dimethylanilinium tetrakis(pentafluorophenyl)borate, [PhMe2NH][B(C6F5)4], tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, [Bu3NH][B(C6F5)4], dimethylanilinium tetrakis(2,3,5,6-tetrafluorophenyl)borate, [PhMe2NH][B(2,3,5,6-C6F4H)4], dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, [PhMe2NH][B(3,5-(CF3)2C6H3)4], dimethylanilinium tetralis(4-fluorophenyl)borate, [PhMe2NH][B(4-C6H4F)4], dimethylanilinium tetraphenylborate, [PhMe2NH][B(C6H5)4], triphenylcarbonium tetrakis(pentafluorophenyl)borate, [Ph3C][B(C6F5)4], ferrocenium tetrakis(pentafluorophenyl)borate, [(C5H5)2Fe][B(C6F5)4], silver tetrakis(pentafluorophenyl)borate, [Ag][B(C6F5)4], and the neutral, strongly Lewis-acidic compounds tris(pentafluorophenyl)borane, B(C6F5)3, tris(2,3,5,6-tetrafluorophenyl)borane, B(2,3,5,6-C6F4H)3, and trimethylboron, BMe3.
The present invention further comprises a catalyst composition comprising a first component which is a compound according to any of formulas (III), (V), (VII), (IX), (XI) or (XIII) or dimers thereof, in which the symbol X represents a halogen atom, and a second component comprising methylaluminoxane (MAO).
The catalyst composition may be formed by mixing together the two components, preferably in a solution in a suitable non-polar solvent such as toluene, benzene, chlorobenzene, an alkane or an alkene, to form a liquid catalyst system.
When the second component is an ionic or neutral compound of the type [PhMe2NH][B(C6F5)4] or B(C6F5)3 then the two components are generally employed in substantially equimolar amounts, although the molar ratio of the first component to the second component may vary within the range of from 0.1 to 5.0. When the second component is methylaluminoxane (MAO) then the second component is employed in large excess, generally in the range from a 100 to 10,000 molar equivalent excess.
Such a quantity of the catalyst system is usually employed in the reaction mixture as to contain from 10xe2x88x921 to 10xe2x88x927 gram atoms, in particular from 10xe2x88x923 to 10xe2x88x925 gram atoms, of the metal per mole of the olefin to be reacted.
The two-component catalyst composition may be formed prior to its introduction tD the reaction vessel, or it may be formed in situ.
Although not required for catalytic activity, further components may be added to the catalytic composition according to the invention, for example in order to increase the solubility and/or the stability of the composition. Organoaluminum compounds in relatively small amounts are efficient scavenging agents.
Examples of such organoaluminum compounds are trimethylaluminum, triethylaluminum, tri-iso-propylaluminum, tri-iso-butylaluminum, triphenylaluminum and diethylaluminum chloride.
The complete catalyst composition according to the invention can be used in solution. Alternatively, the catalyst composition can be loaded onto a solid carrier, in particular an inorganic oxide such as silica, alumina, silica/alumina, titania, zirconia, magnesia and the like, but resinous support materials such as polyolefins can also be used.
The reaction is generally, although not necessarily, carried out in an inert liquid which is suitably also the solvent for the catalyst components. The reaction is suitably carried out at a moderate temperature, preferably in the range of xe2x88x9220 to +150xc2x0 C., more preferably at +10 to +100xc2x0 C. The reaction is suitably carried out under conditions of atmospheric pressure or moderately elevated pressure, preferably in the range from 100 to 10000 kPa.
Reaction times of from 1 minute to 5 hours have been found to be suitable, depending on the activity of the catalyst system and on the reaction conditions. After a suitable reaction time a conventional catalyst deactivating agent such as water, methanol or another alcohol may be added if desired to the reaction mixture in order to terminate the reaction. Alternatively, the reaction can simply be terminated by the introduction of air.
The remaining description of the present invention includes three distinct sections: (1) synthesis of electron-withdrawing amine ligands; (2) attachment of such a ligand to a metal center; and, (3) use of these metal-containing complexes as catalysts for polymerization reactions.
The ligand synthesis portion of the present invention consists of a number of synthetic routes which can be used to prepare the amine ligands which bear electron-withdrawing substituents. In many instances the synthetic procedures themselves are analogous to procedures in the literature, with the starting materials being selected for the purpose of the invention so as to produce the desired amine product. Reference is given in the appropriate section to any compounds previously reported in the literature.
The most commonly employed electron-withdrawing groups are the halogens (fluorine, chlorine, bromine and iodine), trifluoromethyl, cyano and nitro. The drawback with the cyano group is that it has a nitrogen atom which is capable of coordinating strongly to a metal center and thus inhibiting the coordination of olefin. A similar argument applies to the nitro functionality. Among the halogens, Cxe2x80x94I and Cxe2x80x94Br bonds are rather weak and may be subject to cleavage by early transition metal centers. This leaves fluorine, chlorine and trifluoromethyl as the most useful groups. In addition to these simple functionalities, more complex groups such as methylsulfonyl (xe2x80x94SO2Me), its halogenated derivatives (xe2x80x94SO2CF3, xe2x80x94SO2C2F5, xe2x80x94SO2C4F9 etc.) and S-(trifluoromethyl)-N-[(trifluoromethyl)sulfonyl]sulfoximides (xe2x80x94SO(xe2x95x90NSO2CF3)CF3) are powerfully electron-withdrawing and may be utilized as part of the amide ligands.
The mono- or bidentate amide ligands offer a great deal of control over the electrophilicity of the metal center. Thus, on a typical silicon-bridged bis-anilide ligand anywhere from zero to ten electron-withdrawing groups can be incorporated simply by choosing the appropriate substituted aniline from which to begin the synthesis. The ligands are generally easy to prepare from starting materials which are available commercially.
In the following discussion, EW represents an electron withdrawing group.
(a) Monodentate Amines of the Type (EW)NH2 and (EW)2NH
(i) Substituted diphenylamines 
This class of compounds can be prepared by reaction of a substituted fluorobenzene derivative with lithium amide in refluxing tetrahydrofuran (THF). Such a procedure has been used previously to prepare the amine in which X1=X2=X3=X4=X5=F (see Koppang, R. Acta Chem. Scand. 1971, 25, 3067).
Bis(3,5-bis(trifluoromethyl)phenyl)amine (X1=X3=X5=H, X2=X4=CF3) has been described previously as an intermediate in the preparation of optical whiteners and anti-inflammatories (British Patent 1,223,945) and preparation of this compound can be achieved by reaction of 3,5-bis(trifluoromethyl)fluorobenzene (see Kol et. al., J. Am. Chem. Soc. 1994, 116,4382) with lithium amide in THF.
(ii) Unsymmetrical Substituted diphenylamines 
This class of compounds may be prepared by reaction of a substituted fluorobenzene derivative with one equivalent of a lithiated aniline in THF solvent. This procedure has been employed previously to prepare the compound in which X1=X2=X4=X5=F, X3=H, R=H (see Koppang, Fluorine Chem. 1975, 5, 323) and X1=X2=X3=X4=X5=F, R=H (see Koppang, J. Organomet. Chem. 1972, 46, 193).
Alternatively, this class of compounds may be prepared by treating equimolar quantities of a substituted aniline and a fluorobenzene derivative with sodium hydride in dimethylformamide at low temperature: 
This synthetic procedure has been used to prepare the compounds where X1=X2=X4=X5 X6=X7=X8=X9=X10=F or Cl, X3=F or CF3 (see Barlow et. al., German Patent DE 2,213,081). 
A third alternative for the preparation of pentafluorophenyl derivatives is the thernolysis of pentafluorophenyl azide with a 1,3,5-trisubstituted benzene. This synthetic route has been used previously to prepare the compound in which R=R1=Me (see Banks et al., J. Fluorine Chem. 1985, 30: 211).
(iii) Perfluoroalkylsulfonyl amides and bis(perfluoroalkylsulfonyl) amides 
Synthetic procedure A follows that of Roesky, Inorg. Nucl. Chem. Lett. 1970, 6, 807, and may be used to prepare perfluoroalkylsulfonyl amides of the type CnF2n+1SO2NH2 where n is a number between 1 and 12. The preparation of bis(perfluoroalkylsulfonyl) amides will be achieved by the use of procedure B (see Meussdoerffer et. al., Chem. -Ztg. 1972, 96, 582 and Niederpruem et al., German Patent DE 2239817), with n being a number between 1 and 12.
(iv) Bis(perfluoroalkyl)amines 
The compound HN(C2F5)2 has been prepared using the synthetic procedure given above (see Peterman et al., Inorg. Chem. 1975, 14, 1223). This compound can be prepared using such a procedure.
(v) Mono-perfluoroalkylsulfonyl-substituted anilines 
The preparation of 2-trifluoromethylsulfonyl aniline may be accomplished following the above synthetic route of Yagupol""skii et al., Zh. Obshch. Khim. 1967, 37, 2101. This compound can be prepared, together with sulfonyl groups containing longer CnF2n+1 chains. These larger perfluciroalkyl groups could be substituted for xe2x80x94CF3 by starting the synthetic procedure from 4-(HO2C)C6H4(SCnF2n+1) where n=2 to 12.
(vi) Di-perfluoroalkylsulfonyl-substituted anilines 
The preparation of 3,5-bis(trifluoromethylsulfonyl) aniline may be accomplished following the synthetic route of Boiko et al., Zh. Org. Khim. 1985, 21, 1470. This compound can be prepared, together with sulfonyl groups containing longer CnF2n+1 chains. Other perfluoroalkyl groups could be substituted for xe2x80x94CF3 by performing the photolysis step in the presence of longer chain CnF2n+1 compounds, where n=2 to 12.
(vii) Tri-perfluoroalkylsulfonyl-substituted anilines 
The preparation of 2,4,6-tris(trifluoromethylsulfonyl) aniline may be accomplished following the synthetic route of Booth, Synth. Commun. 1983, 13, 659 and Boiko et al., Zh. Org Khim. 1979, 15, 1245. This compound can be prepared, together with sulfonyl groups containing longer CnF2n+1 chains. These larger perfluoroalkyl groups could be substituted for xe2x80x94CF3 by performing the photolysis step in the presence of longer chain CnF2n+1 I compounds, where n=2 to 12.
(viii) Mono S-(perfluoroalkyl)-[N-(perfluoroalkyl)sulfonyl]sulfoximido anilines 
The preparation of 4-[S-(trifluoromethyl)-N-(trifluoromethyl)sulfonyl]sulfoximido aniline may be accomplished following the synthetic route of (i) Movchum et al., J. Fluorine Chem. 1995, 70, 255, (ii) Kondratenko et al., Zh. Org. Khim. 1984, 20, 2250 and (iii) Kondratenko et al., Zh. Org. Khim. 1986, 22, 1716. This compound can be prepared following the above procedure.
(ix) Polyfluoroaryl trialkylsilyl amines or trialkylstannyl amines or trialkylgermyl amines 
This class of compounds may be prepared by reaction of the lithium salt of a substituted aniline with a trialkylchlorosilane or triarylchlorosilane, -stannane or -germane. The use of this synthetic procedure to prepare the compound in which X1=X2=X3=X4=X5=F, E=Si and described previously (see Oliver et al., J. Organometal. Chem. 1969, 19, 17).
(x) Perfluoroalkylsulfonyl trialkylsilyl amines
This class of compounds may be prepared by the reaction of one equivalent of a perfluoroalkylsulfonyl amide with one equivalent of a trialkylchlorosilane, -stannane or -germane in the presence of an excess of a trialkylamine, in a solvent such as diethyl ether. The use of this synthetic procedure to prepare the compound in which R=Me, E=Si and n=1 has been described previously (see Roesky et al., Z. Naturforsch. B 1970, 25, 773). 
The reaction may also be accomplished by treatment of a perfluoroalkylsulfonyl amide with sodium hydride, to form the mono-sodium salt, followed by reaction with a trialkylchlorosilane, -stannane or -germane: 
(b) Bidentate amines of the Type [(EW)NH]2BR2 
(i) Bis(anilino)dialkylsilanes or bis(anilino)diarylsilanes, -stannanes or -germanes (EW=substituted aniline, T=Si, Ge, Sn, R=alkyl or aryl group)
This class of complexes may be prepared using a straightforward reaction of two equivalents of the lithium salt of the substituted aniline with one equivalent of a dichlorodialkylsilane or dichlorodiarylsilane (or the corresponding tin or germanium compounds): 
Deprotonation of the aniline may also be achieved using an alternative alkali-metal reagent such as sodium hydride or potassium hydride.
An alternative synthesis of this class of ligands involves the direct reaction of two equivalents of the substituted aniline with one equivalent of a dichlorodialkylsilane or dichlorodiarylsilane (or the germanium or tin analogs) in an inert solvent such as toluene or benzene, in the presence of a trialkyl amine such as trimethylamine or triethylamine. For examples of this procedure applied to alkyl-substituted anilines, see Takiguchi et al., Bull. Chem. Soc. Japan 1969, 42, 2708 and Anderson, J. Am. Chem. Soc. 1951, 73, 5802. 
A third method of synthesis involves the reaction of a diaminosilane, -stannane or -germane with two equivalents of an alkyllithium reagent to form the dilithio salt, followed by reaction with a suitably substituted aromatic ring: 
This synthetic method would have rather limited applicability due to the difficulty of carrying out aromatic nucleophilic substitution, and the addition of tetramethylethylenediamine (TMEDA) may be required in the second step to increase the nucleophilicity of the diaamine salt. The synthetic method is likely to be most applicable in the case where Y is a fluorine substituent, and the method may work well when X1-X5 and Y are all fluorine substituents.
A fourth synthetic route involves the thermolysis of an alkyl-substituted cyclopolysilane compound in the presence of a substituted aniline: 
This synthetic procedure has been utilized previously to prepare the silicon-bridge bis-aiailine compound in which R=Me, X1=X2=X4=X5=H and X3=Cl (see Dejak et al., Bull. Pol. Acad. Sci. Chem. 1987, 35, 121).
(ii) Bis(alkylamino)dialkylsilanes or bis(alkylamino)diaryl-silanes, -stannanes or -germanes (EW=substituted alkyl amine, B=Si, Ge, Sn, R=alkyl or aryl group)
Preparation of this class of compounds is similar to that described above for bis(anilino)dialkylsilanes and bis(anilino)diarylsilanes. Thus the most useful synthetic route will be the reaction of two equivalents of the lithium salt of the substituted amine with a dichlorodialkylsilane or dichlorodiarylsilane: 
Deprotonation of the substituted amine may also be achieved using an alternative alkali-metal reagent such as sodium hydride or potassium hydride.
In the above equation, each EW maybe independently SO2CnF2n+1 (n=1-12), C1-C10 alkyl or C3-C10 cycloalkyl with any of the alkyl groups bearing one or more halogen atoms e.g. CF3, CH(CF3)2 C4F9 and the like, or Si(R3)3; each R3 being independently chosen from the group of C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl. The groups denoted by R may be independently H, F, C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl with any of these alkyl or aryl groups bearing one or more halogen atoms e.g. C6F5, 3,5-(CF3)2C6F3, CF3, C4F9 and the like.
These compounds may also be prepared by direct reaction of two equivalents of the substituted amine with one equivalent of a dichlorodialkyl-silane or dichlorodiaryl-silane, -stannane or -germane in an inert solvent such as toluene or benzene, in the presence of a trialkyl amine such as trimethylamine or triethylamine: 
A third method of synthesis involves the reaction of a diamino-silane, -stannane or -germane with two equivalents of an alkyllithium reagent to form the dilithio salt, followed by reaction with a halide or triflate derivative of the desired electron-withdrawing group (i.e. J is a good leaving group): 
This method is more useful than the analogous procedure for preparing bis-anilines due to the facile nature of nucleophilic aliphatic substitution compared to aromatic substitution. This method will be particularly useful for preparing derivatives in which EW is a trialkyl- or triaryl-silyl moiety, in which case J would most probably be chloride.
The fourth synthetic route involves the thennolysis of an alkyl-substituted cyclopolysilane compound in the presence of the desired amine: 
(iii) Bis(anilino)methylenes (EW substituted aniline, B=C, R=H) 
The most versatile method for preparing this class of compounds (shown in the equation above) is described by Barluenga et al., Chem. Ber. 1988, 121, 1813 and Barluenga et al., J. Chem. Soc., Perkin Trans. I 1988, 1631. This involves first making a methoxymethyl derivative of the substituted aniline by reacting it with sodium methoxide in methanol followed by reaction with paraformaldehyde. In the second part of the procedure, one equivalent of the lithium salt of a substituted aniline is allowed to react with an equimolar quantity of the methoxymethyl-substituted aniline. It may be noted that symmetrical as well as unsymmetrical bis-aniline compounds may be prepared using this method.
A second method to prepare this class of compounds involves the one-pot reaction of the substituted aniline with potassium hydroxide, ethanol and paraformnaldehyde. This method has been described in the literature (Wakae et al., Osaka Furitsu Kogyo-Shoreikan Hokoku 1963, 29, 47), and is only suitable for the preparation of symmetrical bis-aniline compounds: 
(c) Bidentate amines of the Type [(EW)NH]2C=N(EW) 
(i) Guanidines Bearing Three Substituted Aromatic Rings 
This class of compounds may be prepared following the reaction of substituted N-phenylcarbonimidoyl dichlorides with substituted anilines, using the synthetic procedure of (i) Kolesnikova et al., Zh. Org. Khim. 1989, 25, 1689, (ii) Mikhailov et al., Zh. Org. Khim. 1989, 25, 1683 and (iii) Kolesnikova et al., J. Fluorine Chem. 1988, 40, 217.
The substituted N-phenylcarbonimidoyl dichlorides are prepared by reaction of the desired substituted aniline with aluminum trichloride in tetrachloromethane solvent, using the synthetic procedure of Savchenko et al., J. Fluorine Chem. 1983, 22, 439: 
This class of substituted guanidine compounds may also be prepared from the thiourea derive by treatment with potassium superoxide in THF or acetonitrile solution at low temperature: 
This synthetic procedure has been used to prepare the substituted guanidine in which X1=X2=X4=X5=H, X3=Cl (see Kim et al., J. Chem. Soc., Chem. Commun. 1983, 715).
Alternatively, the thiourea compound may be treated with one equivalent of an iminophosphorane: 
This synthetic procedure has been used to prepare the substituted guanidine in which X1=X2=X4=X5=X6=X7=X9=X10=H, X3=X8=Cl (see Molina et al., Synth. Commun. 1983, 13 67).
Another method of synthesis of guanidine complexes is to treat a mercuric chloride-isocyanide complex with an excess of primary or secondary amine: 
This synthetic procedure has been used to prepare the substituted guanidine in which X1=X5=Me, X2=X3=X4=H, EW=nxe2x80x94Bu (see Sawai et al., J. Organomet. Chem. 1975, 94, 333).
(ii) Guanidines Bearing Two Substituted Aromatic Rings and One Alkyl Group
This class of compounds may be synthesized from the corresponding thiourea compound, by reaction with an alkylamine in the presence of copper(II) sulfate, silica and triethylamine. This procedure is reported by Ramadas et al., Tetrahedron Lett. 1995, 36, 2841. 
The substituted thiourea compounds can in turn be synthesized from a two equivalents of a substituted aniline and carbon disulfide, or by reaction of an aniline derivative with a substituted isothiocyanate compound.
(d) Tetradentate tetra(anilino)-silanes or tetra(alkylamino)-silanes, -germanes or -stannanes 
This class of compounds may be prepared most conveniently by reaction of four equivalents the lithium salt of a substituted aniline with one equivalent of the appropriate Group 14 tetrahalide. 
This synthetic procedure has been reported previously to prepare the tetra(anilino)-silanes, -germanes or -stannanes in which X1=X2=X3=X4=X5F, T=Si (see Jansen et al., Z. Anorg. Allg. Chem. 1992, 610, 99), X1=X2=X3=X4=H, X5=F, T=Si (see Mokros et al., Monatsh. Chem. 1996, 127, 117) and X1=X2=X3=X4=H, X5=Cl, T=Si (see Pikies et al., Anorg. Allg. Chem. 198, 521, 173).
The same synthetic route may also be employed to prepare tetra(alkylamino)silanes, where each EW maybe independently SO2CnF2n+1(n=1-12), C1-C10 alkyl, C6-C15 aryl, or C3-C10 cycloalkyl with any of the alkyl groups bearing one or more halogen atoms e.g. CF3, CH(CF3)2, C4F9 and the like, or Si(R3)3; each R3 being independently chosen from the group of C1-C10 alkyl, C6-C15 aryl, C3-C10 cycloalkyl or alkylaryl. 
Both classes of compounds may also be prepared by reaction of four equivalents of the appropriate amine with a Group 14 tetrahalide in an inert solvent in the presence of a trialkylamine such as trimethylamine or triethylamine: 
(e) 1,2-Diamines Substituted by Electron Withdrawing Groups 
(i) Compounds where Txe2x80x94Txe2x80x94Ax Represents an Aromatic Group
The first synthetic method which will be utilized to prepare this class of compounds is the reaction of 1,2-phenylenediamine (or a substituted derivative thereof) with two equivalents of a substituted fluorobenzene. The reaction is performed in a polar solvent such as dimethyl sulfoxide, the presence of an excess of potassium carbonate. 
This synthetic procedure has previously been employed to prepare pentafluorophenyl-substitui amine ligands by Kol et al., J. Am. Chem. Soc. 1994, 116,4382.
In a second procedure, which is most valuable for preparing derivatives in which the 1,2-diaminobenzene backbone is fully fluorinated, hexafluorobenzene is allowed to react with two equivalents of a substituted aniline in the presence of lithium amide, in a highly polar solvent mixture such as hexamethylphosphoramide/tetrahydrofuran. 
This synthetic route has been employed previously to prepare the compound in which X1=X2=X3=X4=X5=H (see Koppang, Acta Chem. Scand. 1971, 25, 3872). A third route to this class of compounds may be the reaction of 1,2-diiodobenzene (or a substituted derivative thereof) with two equivalents of a substituted aniline in the presence of copper and copper(I) iodide in a high boiling solvent such as dibutyl ether. This procedure has been employed previously to prepare the compound in which X1=X2=X3=X4=H, X5=COMe. (see Hellwinkel et al., Liebigs Ann. Chem. 1985, 1501). 
A fourth route is to react a substituted 1,1,2-triphenylhydrazine with liquid sulfur dioxide (as described by Nojima, Asahi Garasu Kogyo Gijutsu Shoreikai Kenkyu Hokoku 1978, 32, 51; Chem. Abs. 91:175299): 
(ii) Compounds with a saturated hydrocarbon bridge (Bxe2x80x94Bxe2x80x94Ax may represent C3-C10 cycloalkyl, or x=0 and B represents a substituted carbon or silicon atom. B may also represent a chiral carbon atom).
This class of compounds may be prepared by reacting the 1,2-diamine compound (or substituted derivative thereof) with two equivalents of an aromatic group bearing a fluorine substituent on the ring. The reaction is performed in a polar solvent such as dimethyl sulfoxide, in the presence of an excess of potassium carbonate. 
This synthetic procedure has previously been employed to prepare pentafluorophenyl-substituted amine ligands by Kol et al., J Am. Chem. Soc. 1994, 116, 4382. The class of compounds in which Txe2x80x94Txe2x80x94Ax represents a cycloalkyl group may be prepared by treating a cycloalkene with two equivalents of substituted aniline in the presence of mercuric oxide/tetrafluoroboric acid: 
This procedure has been used previously to prepare the compound in which T=CH, A=CH2, x=4, X1=X2=X3=X4=X5=H (see Barluenga et al., Synthesis 1979, 962). The same reaction may also be achieved by replacing the mercuric oxide salt with either mercuric acetate (Hg(O2CCH3)2) (see Gomez et al., Rev. Acad. Cienc. Exactas, Fis.-Quim. Nat. Zaragoza 1974, 29, 321) or thallium(III) acetate (Tl(O2CCH3)3) (see Gomez et al., Synthesis 1974, 504).
The alkene used in the above reactions is not limited to cycloalkenesxe2x80x94it may also be ethylene, propene, styrene, butadiene and the like.
The class of compounds in which x=0 and T represents a methylene group may be prepared by reaction of oxalyl chloride with a substituted aniline in THF, followed by treatment with sodium borohydride powder and trifluoroacetic acid (as described by Nutaitis, C. F. in Synth. Commun. 1992, 22, 1081): 
The class of compounds in which x=0 and T represents a substituted methylene group may be prepared by the reductive coupling of two equivalents of an N-benzyl-substituted aniline using a zinc-copper couple as the reducing reagent. 
This reaction has been performed in the presence of optically pure camphorsulfonic acid, and this has been used as a method of preparing the chiral diamine in which X1=X2=X5=H, X3=OMe (see Shimizu et al., Chem. Lett. 1995, 609).
In the polymerization of propene, and other prochiral olefins, the presence of a chiral ligand on the metal center may be highly desirable in order to control the molecular architecture of the growing polymer chain, i.e., to produce isotactic or syndiotactic polymers. One aspect of the present invention is the placement of chiral diamine ligands onto a transition metal or lanthanide metal center such that they will influence the mode of attachment of each successive monomer unit to the growing polymer chain.
Such chiral diamines may be prepared in two principal ways:
(i) A reaction is performed which produces both optical isomers of the desired product; the isomers then separated (or resolved) by means of reaction with a pure optical isomer of a second chiral compound such that a pair of diastereoisomers is produced. The diastereoisomers are then separated by repeated fractional crystallization.
(ii) The reaction is performed by placing the desired electron-withdrawing functional groups onto a pure optical isomer of a precursor diamine ligand such as 1,2-diaminocyclohexane or 2,3-diphenyl-2,3-diaminobutane.
Resolution of the chiral amine in which X1=X2=X4=X5=H, X3=F has been described previously (see Collet et al., Bull. Soc. Chim. Fr. 1972, 336.
This class of compounds may also be prepared by the reductive coupling of two equivalents of an imine using a range of reducing reagents. This procedure normally results in the formation of a mixture of the meso- and rac-forms of the diamine. Separation of these two isomers by crystallization can produce a pure sample of the rac (or dl) form of the diamine. Subsequent reaction of the rac compound with an optically pure isomer of a suitable resolving reagent can allow separation of the R,R and S,S enantiomers of the diamine: 
The example given above employs a solution of samarium diiodide in THF to couple the two imines, and this procedure has been reported for the compound in which X8=Cl and all other X=H (see Inamoto et al., Kidorui 1990, 16, 80) and also for the compound in which X1-X10=H (see Imamoto et al., Chem. Lett. 1990, 1141).
The use of aluminum/bismuth powder and potassium hydroxide in methanol at ambient temperature has been reported in the synthesis of the diamine in which X7=Cl and all other X=H (see Baruah et al., Tetrahedron Lett. 1995, 36, 6747).
The use of indium metal in aqueous solution has been reported in the synthesis of the compound in which X6=Cl and all other X=H (see Kalyanam et al., Tetrahedron Lett. 1993, 34, 1647).
The use of zinc dust and ammonium chloride as a reducing/coupling reagent has been reported in the synthesis of the compound in which X6=Cl and all other X=H (see Kumar et al., Indian J. Chem., Sect. B 1991, 30B, 1069).
Another method of preparing a mixture of meso and d,l isomers of a 1,2-diamine ligand has been described by Katritzky et al (J. Org. Chem. 1990, 55, 3209). This procedure entails the reaction of the desired amine with glyoxal and benzotriazole in ethanol to produce an intermediate bis-benzotriazole complex: 
In a second step, two equivalents of a Grignard reagent are added to the benzotriazole complex to produce a 1,2-diamine with bulky R* groups on the backbone and the desired aromatic groups attached to nitrogen. 
A further synthetic method for producing this class of compounds (Bambridge, K. et al Tetrahedron Lett. 1994, 35, 3391 and Neumann, W. L. et al Tetrahedron Lett. 1991, 32, 5865) entails the reaction of glyoxal with an amine (which may be chiral) to produce a bis-imine compound: 
Further reaction of the bis-imine with two equivalents of Grignard reagent allows the isolation of a substituted 1,2-diamine compound. When a chiral amine is employed in the first step, the addition of the Grignard reagent is highly diastereoselective, resulting in the predominant formation of the C2-symmetrical d,l isomer. 
(f) 1,3-Diamines substituted by electron withdrawing groups 
(i) Compounds where Txe2x80x94Txe2x80x94Txe2x80x94Axxe2x80x94Jxxe2x80x94Gx represents an aromatic group
The first synthetic method which will be utilized to prepare this class of compounds is the reaction of 1,8-diaminonaphthalene (or substituted derivative thereof) with two equivalents of an aromatic group bearing a fluorine substituent on the ring. The reaction is performed in a polar solvent such as dimethyl sulfoxide, in the presence of an excess of potassium carbonate. 
An alternative synthetic route would involve the preparation of a substituted perimidinone, and the reaction of this with a substituted iodobenzene in the presence of copper. The molecule is then decarboxylated using methyllithium to give the 1,8-diaryl-substituted diaminonaphthalene (see Rimmler et al., Chem. Ber. 1992, 125, 723): 
(ii) Compounds with a saturated three-carbon linkage
This class of compounds may be prepared by reacting two equivalents of the lithium salt of a substituted aniline with 1,3-dibromopropane in the presence of tetramethylethylenediamine. This procedure has been employed previously to prepare the compounds in which X2=X3=X4=H, X1=X5=Me or i-Pr (see Scollard et al., Organometallics 1995, 14, 5478). 
Preparation or placement of the mono- or diamine ligand system onto a metal center can be achieved in a number of ways, as described below. In the following figures, the example of a two-carbon bridged bis-amine ligand is used, but the preparative procedures apply equally to the entire range of amine-containing ligands described in the previous sections. R1 and R2 represent electron-withdrawing groups.
(i) Deprotonation of the amine ligand with an alkyllithium reagent or sodium hydride or potassium hydride, followed by reaction with an anhydrous metal halide salt, as shown in the general scheme below; 
Due to the electron-withdrawing nature of the substituents R1 and R2, the xe2x80x94NH protons are relatively acidic and therefore react vigorously with reagents such as alkyllithium and sodium or potassium hydride. Thus, the deprotonation reactions are best carried out at low temperature (xe2x88x9230xc2x0 C. or below). It is also found that the second step of the reaction, i.e. the treatment of the dilithiated amine with the metal halide, is also best carried out at low temperature (xe2x88x9230xc2x0 C. or below). The reaction is typically performed in a solvent such as diethyl ether or tetrahydrofuran.
(ii) Reaction of the amine ligand with an amide- or alkyl-containing complex of the metal, so as to protonate the amide or alkyl group(s); 
If the reaction is performed with a metal tetrakis(amide) complex (i.e. X=NR2) then the reaction is a transamination, and the reaction mixture may have to be heated in order for the reaction to proceed. Typical temperature for the reaction mixture would be in the range from 20xc2x0 C. to 100xc2x0 C. The solvent employed is usually an inert, non-donor solvent such as benzene, toluene or heptane.
If a metal tris- or tetrakis-(alkyl) complex is employed as the starting material, then heating is not normally required. In this case the reaction mixture would be stirred for one to twelve hours at ambient temperature before being subjected to a work-up procedure.
Preparation of the active catalyst species may also be accomplished in a number of ways:
(i) A metal bis-alkyl species may be reacted with one equivalent of a proton-donating cation, to protonate off one alkyl group as an alkane and leave a cationic metal complex together with a bulky, non-coordinating anion: 
The reaction would typically be performed at room temperature in a non-donor solvent such as benzene, toluene or hexane.
(ii) A metal dihalide complex may be allowed to react with methylaluminoxane, which serves the dual purpose of alkylating the metal center and subsequently abstracting an alkyl group to leave the desired cationic species: 
The reaction would typically be performed at room temperature in a non-donor solvent such as benzene, toluene or hexane.
(iii) A powerfully Lewis-acidic neutral reagent such as B(C6F5)3 may be added in order to abstract an alkyl anion from the metal center and produce the active cationic metal complex. The counter anion would then be a bulky species such as [BMe(C6F5)3]xe2x88x92. 
The reaction would typically be performed at room temperature in a non-donor solvent such as benzene, toluene or hexane.
(iv) A powerfully Lewis-acidic cationic reagent such as the trityl (triphenylmethyl) cation may be added in order to abstract an alkyl anion from the metal center and produce the active cationic metal complex. The counter anion would then be a bulky species such as [B(C6F5)4]xe2x88x92 
The reaction would typically be performed at room temperature in a non-donor solvent such as benzene, toluene or hexane.
A typical polymerization reaction employing method (i) above would be carried out as follows: into a glass vessel (in the drybox) is placed approximately 50 ml of toluene and 5 mg of the dimethyl derivative of the bis-amide metal complex and the solution stirred until the solid dissolves. The vessel is sealed with a septum and removed from the drybox. Into a second glass vessel (in the drybox) is placed 10 ml of toluene and a quantity of the salt [HNMe2Ph][B(C6F5)4] which is equimolar with the amount of metal complex taken. This vessel is sealed and removed from the drybox. Ethylene gas is allowed to purge through the metal-containing toluene solution for 5 minutes to saturate the solution, and then using a syringe the toluene solution of the ammonium salt is added rapidly. Ethylene is allowed to bubble through the solution for a set period of time (several minutes usually) and then methanol is added to the reaction mixture to destroy the catalyst and terminate the reaction. The polyethylene is then filtered off, washed with methanol, water and hydrochloric acid, and dried in a vacuum oven to constant weight.
A typical polymerization reaction employing method (ii) above would be carried out as follows: into a glass vessel (in the drybox) is placed approximately 10 ml of toluene, 5 mg of the dichloro derivative of the bis-amide metal complex and an approximately 500-fold molar excess of methylaluminoxane solution in toluene. The vessel is sealed with a septum and removed from the drybox. Into a second glass vessel (in the drybox) is placed 40 ml of toluene and a quantity of methylaluminoxane equal to that added to the metal complex. This vessel is sealed and removed from the drybox. Ethylene gas is allowed to purge through the toluene/methylaluminoxane solution for 5 minutes to saturate the solution, and then using a syringe the toluene solution of the metal complex/methylaluminoxane is added rapidly. Ethylene is allowed to bubble through the solution for a set period of time (several minutes usually) and then methanol is added to the reaction mixture to destroy the catalyst and terminate the reaction. The polyethylene is then filtered off, washed with methanol, water and hydrochloric acid, and dried in a vacuum oven to constant weight.